This invention relates to the catalytic hydroprocessing of heavy hydrocarbon oils including crude oils, heavy crude oils and residual oils as well as refractory heavy distillates, including FCC decanted oils and lubricating oils. It also relates to the hydroprocessing of shale oils, oils from tar sands, and liquids derived from coals. The invention relates to a catalyst for the hydroprocessing of such hydrocarbonaceous feedstocks, the use of such catalysts, and the preparation of such catalysts.
In U.S. application Ser. No. 527,414 filed Aug. 29, 1983 (now U.S. Pat. No. 4,557,821), a parent application of the present application, a catalytic means of hydroprocessing heavy oils was revealed which employs a circulating slurry catalyst. The catalyst comprised a dispersed form of molybdenum disulfide prepared by reacting aqueous ammonia and molybdenum oxide to form an aqueous ammonium molybdate which was reacted with a dosage of hydrogen sulfide to form a precursor slurry. The precursor slurry was mixed with feed oil, hydrogen and hydrogen sulfide and heated under certain conditions. A variety of dosages of hydrogen sulfide expressed as SCF of hydrogen sulfide per pound of molybdenum were taught to be useful in forming the precursor slurry (Column 3). From 2-8 SCF/LB were preferred (Column 4). It was found to be necessary to mix the slurry with oil in the presence of both hydrogen and hydrogen sulfide in order to obtain a catalytically active slurry catalyst (Columns 11-12). The oil-slurry mixture was then sulfided with hydrogen and hydrogen sulfide at at least two temperatures (Column 24) under certain conditions. The feed and catalyst, with water added were charged to the hydroprocessing reactor. Water introduction was deemed beneficial (Columns 26-27) for certain purposes, as was nickel addition to the slurry catalyst (Columns 42-44).
In U.S. application Ser. No. 941,456 filed Dec. 15, 1986 (U.S. Pat. No. 4,857,496), a parent application of the present application, is described a sulfiding process in which there are two or three heating steps providing time-temperature sequences to complete the preparation of the final catalyst prior to flowing the feed to the higher temperature hydroprocessing reactor zone. Each sulfiding step was operated at a temperature higher than its predecessor. Ammonia was removed from an intermediate stage of catalyst preparation before the addition of feed oil and further sulfiding.
U.S. application Ser. No. 767,760 filed Aug. 21, 1985, (U.S. Pat. No. 4,824,821), also a continuation-in-part of U.S. application Ser. No. 527,414 filed Aug. 29, 1983, describes the promotion of a Group VIB slurry catalyst by the addition of a Group VIII metal such as nickel or cobalt, to the aqueous ammonia compound after sulfiding is underway.
U.S. application Ser. No. 767,768 filed Aug. 21, 1985, also a continuation-in-part of U.S. application Ser. No. 527,414 filed Aug. 29, 1983, describes the specific regulation of the amount of sulfiding occurring in intermediate temperature sulfiding steps by stoichiometric replacement of oxygen associated with the Group VIB metal with sulfur up to fifty to ninety-five percent replacement. At least three stages of sulfiding were preferred with additional replacement of oxygen by sulfur in the high temperature step.
U.S. application Ser. No. 767,821 filed Aug. 21, 1985 (U.S. Pat. No. 4,762,812), also a continuation-in-part of U.S. application Ser. No. 527,414 filed Aug. 29, 1983, described a process for the recovery of spent molybdenum catalysts.
A parent application of the present application, U.S. application Ser. No. 275,235 filed Nov. 22, 1988, described a Group VIB metal sulfide slurry catalyst for hydroprocessing heavy oils or residual oil which has a pore volume of 10-300 angstrom radius pore size range of at least 0.1 cc/g.
The specifications of all of the foregoing U.S. patent applications are incorporated herein by reference as if fully set forth in ipsis verbis.